O-alkyl-O-6{8 P-halophenyl{9 -pyridazinyl-{8 3{9 -thiono-phosphoric (phosphonic) acid esters

ABSTRACT

O-alkyl-O-6-(p-halophenyl)-pyridazinyl-(3)-thiono-phosphoric (phosphonic) acid esters of the formula   IN WHICH R is alkyl of 1 to 6 carbon atoms, R1 is alkyl or alkoxy of 1 to 6 carbon atoms or phenyl, and Hal is halogen WHICH POSSESS INSECTICIDAL AND ACARICIDAL PROPERTIES.

United States Patent 1 Lorenz et al.

[5 4 O-ALKYL-O-6[P-HALOPHENYL]- PYRIDAZINYL-[3]-THIONO-PHOSPHORIC (PHOSPHONIC) ACID ESTERS [75] Inventors: Walter Lorenz, Wuppertal; Ingeborg Hammann, Cologne, both of Germany [73] Assignee: Bayer Aktiengesellschaft,

Leverkusen, Germany [22] Filed: Mar. 14, 1973 [21] Appl. No.: 341,189

[30] Foreign Application Priority Data Mar. 23. 1972 Germany 2214059 [52] US. Cl. 260/250 AP; 260/250 A; 424/250 June 24, 1975 Primary Examiner-Donald G. Daus Assistant Examiner.lames H. Turnipseed Attorney. Agent, or Firm-Burgess, Dinklage & Sprung [57] ABSTRACT O-alkyl-O-6-[p-halophenyl]-pyridazinyl-[ 3 l-thionophosphoric (phosphonic) acid esters of the formula in which R is alkyl of l to 6 carbon atoms,

R, is alkyl or alkoxy of l to 6 carbon atoms or phenyl,

and

Hal is halogen which possess insecticidal and acaricidal properties.

7 Claims, No Drawings 1 O -ALKYL-O-6(P-HALOPHENYL)-PYR]DAZINYL- (3)-THIONO-PHOSPHORIC (PHOSPHONIC) ACID ESTERS The present invention relates to and has for its objects the provision of particular new O-alkyl-O-6-[phalophenyl l-pyridazinyl-l 3l-thionophosphoric (phosphonic) acid esters which possess insecticidal and acaricidal properties, active compositions in the form of mixtures of such compounds with solid and liquid dispersible carrier vehicles, and methods for producing such compounds and for using such compounds in a new way especially for combating pests. e.g. insects and acarids, with other and further objects becoming apparent from a study of the within specification and accompanying examples.

It is known from German Published Specification DOS No. 2,043,745 that phenyl-pyridazino(thiono)- phosphoric acid esters, for example 0,0-diethyl-O-6- phenyl-pyridazinyl-(3)-thionophosphoric acid ester (Compound A). possess an insecticidal and acaricidal activity.

mula (l) in which a 3-hydroxypyridazino derivative of the general formula Hal-Q Q-OH is reacted, in the presence of an acid-acceptor or in the form of an alkali metal, alkaline earth metal or ammonium salt thereof, with a thionophosphoric(phosphonic) acid ester halide of the general formula P-Hal i ll Cl-QQ-O-P (00 a 2 2 m 5 (IV) The present invention provides, as new compounds, the halogenophenyl-pyridazino-thiono-phosphoric(- phosphonic) acid esters of the general formula in which R is alkyl of l to 6 carbon atoms,

R is alkyl or alkoxy of l to 6 carbon atoms or phenyl,

and

Hal is halogen.

Preferably, R is lower alkyl of l to 4 carbon atoms, R, is lower alkyl or lower alkoxy of l to 4 carbon atoms or phenyl, and Hal is chlorine or bromine.

Surprisingly, the halogenophenyl-pyridazino-thionophosphoric(phosphonic) acid esters according to the invention possess, in addition to an acaricidal action, a considerably stronger insecticidal action than the known phenyl-pyridazino-(thiono)phosphoric acid esters of analogous structure and identical, type of action. The invention thus represents a genuine enrichment of the art. Furthermore. the compounds of this invention help satisfy the great demand for new active compounds in the field of pesticides. The latter demand results from the fact that the commercially available agents have to meet increasingly stringent requirements particularly with regard to questions of protection of the environment such as low toxicity to warm-blooded animals, low phytotoxicity, rapid degradation in and on the plant in short minimum intervals to be observed between spraying with pesticide and harvesting, activity against resistant pests and the like.

The present invention also provides a process for the production of a halogenophenyl-pyridazinothionophosphoric-(phosphonic) acid ester of the for- The following may be mentioned as examples of thiono-phosphoric(phosphonic) acid ester halides (II) which can be used according to the process: 0.0- u'iethyl-, 0.0-diisopropyl-, 0,0-dibutyl-, 0,0-di tert.- butyl-, O-ethyl-O-isopropyl, O-ethyl-O-propyl-, O- ethyl-O-butyl-, O-isopropyl-O-butyh and O-propyl-O- butyl-thiono-phosphoric acid ester chlorides and bromides, and also O-ethyl-ethane-, O-propyl-ethane-, O-isopropyl-ethane-, O-ethyl-propane-, O-ethylisopropane-, O-ethyl-butane-. O-isopropyl-propane-, O-ethyl-phenyl-, O-isopropyl-phenyland O-butylphenyl-thiono-phosphonic acid ester chlorides and bromides.

Examples of pyridazino derivatives III) which can be used according to the process are: 6-(p-chloroor pbromo-phenyl)-3-hydroxypyridazine or their 3-keto tautomers.

The acid halides and pyridazine derivatives which are to be used are known and can be prepared in accordance with customary methods.

Possible solvents or diluents for carrying out the process are practically all inert organic solvents, especially aliphatic and aromatic, optionally chlorinated hydrocarbons, such as benzene. toluene. xylene, benzine, methylene chloride, chloroform, carbon tetrachloride and chlorobenzene; ethers, for example diethyl ether, dibutyl ether and dioxane; ketones, such as acetone, methyl ethyl ketone, methyl isopropyl ketone and methyl isobutyl ketone; and nitriles, preferably acetonitrile.

Possible acid-acceptors are all customary acidbinding agents. Alkali metal carbonates and alcoholates, such as sodium carbonate. potassium carbonate, sodium methylate, potassium methylate, sodium ethylate and potassium ethylate, and also aliphatic, aromatic or heterocyclic amines, for example triethylamine, dimethylamine. dimethylaniline. dimethylbenzylamine and pyridine. have proved particularly suitable.

The reaction temperatures can be varied over a fairly wide range. In general the reaction is carried out at about lO to 120, preferably at about 60 to 80C.

The reaction is generally carried out under normal pressure.

To carry out the process, the starting components are generally reacted in an equimolar ratio, in one of the above-mentioned solvents, at the indicated temperatures, if appropriate in the presence of an acidacceptor. After stirring the mixture at an elevated temperature for several hours, the mixture is filtered if necessary and poured into water, and the crystalline precipitate which separates out is filtered off, washed and recrystallized.

The compounds according to the invention are obtained in crystalline form and are characterized by their melting points.

As already mentioned, the compounds according to the invention possess coupled with only slight phytotoxicity an excellent insecticidal activity and also an acaricidal activity, against plant pests, pests harmful to health and pests of stored products. Herein, they are distinguished by a good action against both sucking and biting insects and against mites (Acarina).

For these reasons, the compounds according to the invention may be successfully employed as pesticides, especially in plant protection and the protection of stored products, and also in the hygiene field.

The sucking insects combated in the main include aphids (Aphididae) such as the green peach aphid (Myzus persicae), the bean aphid (Doralis fabae), the bird cherry aphid (Rhopalosiphum padi), the pea aphid (Macrosiplzum pisi) and the potato aphid (Macrosiphum solanifolii), the currant gall aphid (Crypromyzus korschelri), the rosy apple aphid (Sappaphis mali), the mealy plum aphid (Hyalopterus arundinis) and the cherry black-fly (Myzus rerasi); in addition, scales and mealybugs (Coccina), for example the oleander scale (Aspidiotus hederae) and the soft scale (Lecanium hes peridum) as well as the grape mealybug (Pseudococcus marin'mus); thrips (Thysanoptera), such as Hereinarlzrips femoralis, and bugs, for example the beet bug (Piesma quadrata), the red cotton bug (Dysdereus intermedius), the bed bug (Cimex lec'mlarius), the assassin bug (Rhodnius prolixus) and Chagas' bug (Triatoma infestans) and, further, cicadas, such as Euscelis bilobams and Nephotettix bipuncrams.

In the case of the biting insects, above all there should be mentioned butterfly caterpillars (Lepidoptera) such as the diamond-back moth (Plutella maculipenm's), the gypsy moth (Lymanm'a dispar), the browntail moth (Euprocn's chrysorrhoea) and tent caterpillar (Malacosoma neusrria); further, the cabbage moth (Mamesrra brassicae) and the cutworm (Agrotis segetum), the large white butterfly ieris brassicae), the small winter moth (C/teimatobia brumala), the green oak tortrix moth (Torm'x vin'dana), the fall armyworm (Laphygma frugiperda) and cotton worm (Prodem'a Iitura), the ermine moth (Hyponomeum padella), the Mediterranean flour moth (Ephesn'a kulmiella) and greater wax moth (Galleria mellonella).

Also to be classed with the biting insects are beetles (Coleoptera), for example the granary weevil (Sirophilus granarius Calandra granaria), the Colorado beetle (Lepitinomrsa decemlineam), the dock beetle (Gasrrophysa viridula), the mustard beetle (Pliaedon cochleariae), the blossom beetle (Meligerhes aeneus),

the raspberry beetle in Mien/mus), the bean weevil (Bruchidius AtwrI/lr)s('1ide5 ubtectus), the leather beetle (Dermemw mrlzi). the khapra beetle Trogoderma granarium). the flour beetle (Tribolium c'asraneum), the northern corn billbug (Calandra or Sitophilus zeamais), the drugstore beetle (Stegobium paniceum), the yellow mealworm (Tenebrio molitor) and the saw-toothed grain beetle (Oryzaephilus- .rurinamensis), and also species living in the soil, for example wireworms (Agriotes spec.) and larvae of the cockchafer (Melolomha melolomha); cockroaches, such as the German cockroach (Blaltella germanica), American cockroach (Periplanera americana), Madeira cockroach (Leucophaea or R/ryparobia maderae), oriental cockroach (Blarra orientalis), the giant cockroach (Blaberus giganreus) and the black giant cockroach (Blaberus fuscus) as well as Henschoutedenia flexivitta; further, Orthoprera, for example the house cricket (Acheta domesricus); termites such as the eastern subterranean termite (Rericulirermes flavipes) and Hymenoptera such as ants, for example the garden ant (Lasius niger).

The Diptera comprise essentially the flies, such as the vinegar fly (Drosophila melanogasrer), the Mediterranean fruit fly (Ceraritis capitata), the house fly (Musca domestica), the little house fly (Fanm'a canicularis). the black blow fly (Phormia regina) and bluebottle fly (Cal- Iiplzora erythrocephala) as well as the stable fly (Stomoxys calcitrans); further, gnats, for example mosquitoes such as the yellow fever mosquito (Aedes uegypti the northern house mosquito (Culex pipiens) and the malaria mosquito (Anopheles stephensi).

With the mites (Acarina) there are classed, in particular, the spider mites (Tetranychidae) such as the twospotted spider mite (Tetranychus urlicae) and the European red mite (Paraterranychus pilosus Panonychus ulmi). gall mites, for example the black-currant gall mite (Eriophyes ribis) and tarsonemids, for example the broad mite (Hemitarsonemus Imus) and the cyclamen mite (Tarsonemus pallidus); finally, ticks, such as the relapsing fever tick (Ornithodorus moubata).

When applied against pests harmful to health and pests of stored products, particularly flies and mosquitoes, the process products are also distinguished by an outstanding residual activity on wood and clay, as well as a good stability to alkali on limed substrates.

The active compounds according to the instant invention can be utilized, if desired, in the form of the usual formulations or compositions with conventional inert (i.e. plant compatible or herbicidally inert) pesticide diluents or extenders, i.e. diluents, carriers or extenders of the type usable in conventional pesticide formulations or compositions, e.g. conventional pesticide dispersible carrier vehicles such as gases, solutions, emulsions, suspensions, emulsifiable concentrates, spray powders, pastes, soluble powders, dusting agents, granules, etc. These are prepared in known manner, for instance by extending the active compounds with conventional pesticide dispersible liquid diluent carriers and/or dispersible solid carriers optionally with the use of carrier vehicle assistants, e.g. conventional pesticide surface-active agents, including emulsifying agents and/or dispersing agents, whereby, for example, in the case where water is used as diluent, organic solvents may be added as auxiliary solvents. The following may be chiefly considered for use as conventional carrier vehicles for this purpose: aerosol propellants which are gaseous at normal temperatures and pressures, such as freon; inert dispersible liquid diluent carriers, including inert organic solvents, such as aromatic hydrocarbons (e.g. benzene, toluene, xylene, alkyl naphthalenes, etc.), halogenated, especially chlorinated, aromatic hydrocarbons (e.g. chlorobenzenes, etc.), cycloalkanes (e.g. cyclohexane, etc.), paraffins (e.g. petroleum or mineral oil fractions), chlorinated aliphatic hydrocarbons (e.g. methylene chloride, chloroethylenes, etc.), alcohols (e.g. methanol, ethanol, propanol, butanol, glycol, etc.) as well as ethers and esters thereof (e.g. glycol monomethyl ether, etc.), amines (e.g. ethanolamine, etc.), amides (e.g. dimethyl formamide, etc.), sulfoxides (e.g. dimethyl sulfoxide, etc.), acetonitrile, ketones (e.g. acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), and/or water; as well as inert dispersible finely divided solid carriers, such as ground natural minerals (e.g. kaolins, clays, alumina, silica, chalk, i.e. calcium carbonate, talc, attapulgite, montmorillonite, kieselguhr, etc.) and ground synthetic minerals (e.g. highly dispersed silicic acid, silicates, e.g. alkali silicates, etc); whereas the following may be chiefly considered for use as conventional carrier vehicle assistants, e.g. surface-active agents, for this purpose: emulsifying agents, such as non-ionic andlor anionic emulsifying agents (e.g. polyethylene oxide esters of fatty acids, polyethylene oxide ethers of fatty alcohols, alkyl sulfates, alkyl sulfonates, aryl sulfonates, albumin hydrolyzates, etc., and especially alkyl arylpolyglycol ethers, magnesium stearate, sodium oleate, etc.), and/or dispersing agents, such as lignin, sulfite waste liquors, methyl cellulose, etc.

Such active compounds may be employed alone or in the form of mixtures with one another and/or with such solid and/or liquid dispersible carrier vehicles and/or with other known compatible active agents, especially plant protection agents, such as other insecticides, acaricides, rodenticides and fungicides, or bactericides, nematocides, herbicides, fertilizers, growth-regulating agents, etc., if desired, or in the form of particular dosage preparations for specific application made therefrom, such as solutions, emulsions, suspensions, powders, pastes, and granules which are thus ready for use.

As concerns commercially marketed preparations, these generally contemplate carrier composition mixtures in which the active compound is present in an amount substantially between about 01-95% by weight, and preferably 05-90% by weight, of the mixture, whereas carrier composition mixtures suitable for direct application or field application generally contemplate those in which the active compound is present in an amount substantially between about 0.000 l-l preferably 0.0ll%, by weight of the mixture. Thus, the present invention contemplates over-all compositions which comprises mixtures of a conventional dispersible carrier vehicle such as (l) a dispersible inert finely divided carrier solid, and/or (2) a dispersible carrier liquid such as an inert organic solvent and/or water preferably including a surface-active effective amount of a carrier vehicle assistant, e. g. a surface-active agent, such as an emulsifying agent and/or a dispersing agent, and an amount of the active compound which is effective for the purpose in question and which is generally between about 0.000l-95%, and preferably 0.0l95%, by weight of the mixture.

The active compounds can also be used in accordance with the well known ultra-low-volume process with good success, i.e. by applying such compound if normally a liquid, or by applying a liquid composition containing the same, via very effective atomizing equipment, in finely divided form, e.g. average particle diameter of from 50-100 microns, or even less, i.e. mist form, for example by airplane crop spraying techniques. Only up to at most about a few liters/hectare are needed. and often amounts only up to about 15 to 1000 g/hectare, preferably 40 to 600 g/hectare, are sufficient. In this process it is possible to use highly concentrated liquid compositions with said liquid carrier vehicles containing from about 20 to about by weight of the active compound or even the active substance alone, e.g. about 20-100% by weight of the active compound.

Furthermore, the present invention contemplates methods of selectively killing, combating or controlling pests, e.g. insects and acarids, which comprises applying to at least one of correspondingly (a) such insects, (b) such acarids and (c) the corresponding habitat thereof, i.e. the locus to be protected, a correspondingly combative or toxic amount, i.e. an insecticidally or acaricidally effective amount, of the particular active compound of the invention alone or together with a carrier vehicle as noted above. The instant formulations or compositions are applied in the usual manner, for instance by spraying, atomizing, vaporizing, scattering, dusting, watering, squirting, sprinkling, pouring, fumigating, dressing, encrustation, and the like.

It will be realized, of course, that the concentration of the particular active compound utilized in admixture with the carrier vehicle will depend upon the intended application. Therefore, in special cases it is possible to go above or below the aforementioned concentration ranges.

The synthesis, unexpected superiority and outstanding activity of the particular new compounds of the present invention are illustrated, without limitation, by the following examples:

EXAMPLE 1 Ceratitis Test Solvent: 3 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, part by weight of the active compound is mixed with the stated amount of solvent containing the stated amount of emulsifier, and the concentrate is diluted with water to the desired concentration. 1 cm of the preparation of the active compound is pipetted onto a filter paper disc of about 7 cm diameter. This is placed on a glass in which there are about 30 fruit flies (Ceratitis capitata) and covered with a glass plate.

After the specified periods of time, the destruction is determined as a percentage. l00% means that all the flies were killed. 0% means that none of the flies were killed.

The active compounds, the concentrations of the active compounds, the evaluation times and the degree of destruction can be seen from the following Table l:

Plutella Test Solvent: 3 parts by weight of acetone Emulsifier: l part by weight alkylaryl polyglycol ether To produce a suitable preparation of active compound. l part by weight of the active compound is mixed with the stated amount of solvent containing the stated amount of emulsifier and the concentrate is diluted with water to the desired concentration.

Cabbage leaves (Brassica olemcea) are sprayed with the preparation of the active compound until dew moist and are then infested with caterpillars of the diamondback moth (Plulella maculipennis).

After the specified periods of time, the degree of destruction is determined as a percentage: 100% means that all the caterpillars are killed whereas means that none of the caterpillars are killed.

The active compounds, the concentrations of the active compounds, the evaluation times and the results can be seen from the following Table 2:

Table 2 Table l (Cemtitis test) Active compound Active compound Degree of concentration in destruction by weight m 7: after I day S ll 0.l @Q- O-P(OC. .H,-,)-

0.02 0 N N (known) (A) S 0.! I00 I) 0.02 100 Cl O-P(OC ,H 0.004 100 0.0008 N N (l) S O.l 100 ll (1.02 100 Sr w 0P(OC H 0.004

EXAMPLE 2 EXAMPLE 3 Myzus Test (contact action) Solvent: 3 parts by weight of acetone Emulsifier: l part by weight alkylaryl polyglycol ether To produce a suitable preparation of active compound, part by weight of the active compound is mixed with the stated amount of solvent containing the stated amount of emulsifier and the concentrate is diluted with water to the desired concentration.

Cabbage plants (Brassica oleracea) which have been heavily infested with peach aphids (Myzus persicae) are sprayed with the preparation of the active compound until dripping wet.

After the specified periods of time, the degree of destruction is determined as a percentage: means that all the aphids are killed whereas 0% means that none of the aphids are killed.

(Plutella test) The active compounds, the concentrations of the active compounds, the evaluation times and the results can be seen from the following Table 3:

l chlorophenyl)-pyridazinyl-(3)-thionophosphoric acid ester are obtained in the form of beige-colored crystals of melting point 97C.

Table 3 (Myzus test) 1 Active compound Active compound Degree of concentration in destruction 1 by weight in K after l day S ll (].l 100 0-P(OC H,-,1. 0.02

(known) N (A) i r s 0.1 [00 0 il 0.02 I00 c1 QQO-HOCJifl-g 0.004 80 N N m s 01 :00 u C. .H 0.02 100 C1 O-P 0.004 98 oc u 0.0008 80 N N 0.000l6 s0 (4) S [00 II 002 I00 OP(OC H 004 40 S l00 N CH, 002 lOO B M04 0.004 s0 OC H a N N [3) The process of this invention is illustrated by the following preparative Example.

Structure 30 The following compounds can be produced in an analogous manner:

Yield of theory) Melting point, C

s It iH.t ct o r 93-94 32.8 M (4) N N cut i 79 EXAMPLE 4 tallized from a mixture of petroleum ether/ethyl acetate. g (45.5% of theory) of 0,0-diethyl-O-6-(p- It will be appreciated that the instant specification and examples are set forth by way of illustration and 55 not limitation. and that various modifications and changes may be made without departing from the spirit and scope of the present invention.

What is claimed is:

1. An O-alkyl-O-6-lp-halogenophenyll-pyridazinyl- 0 [3]thionophosphoric(phosphonic) acid ester of the formula 5 II as QQ Ion (I) in which R is alkyl of l to 6 carbon atoms,

4. The compound according to claim 1 wherein such: compound is 0,0-diethyl-O6-(p-bromophenyl) pyridazinyl-(3 )-thionophosphoric acid ester of the formula 5. The compound according to claim 1 wherein such compound is ethyl-O-ethyl-O-6-(p-bromophenyl)- pyridazinyl-(3 )-thionophosphonic acid ester of the formula l 2 S/CZHS o-Q N-L 6. The compound according to claim 1 wherein such compound is ethyl-O-ethyl-O-6(p-chlorophenylpyridazinyl)-3 )-thionophosphonic acid ester of the formula s z 's G-Q N 7. The compound according to claim 1 wherein such compound is phenyl-O-ethyl-O-6-(p-chlorophenyl)- pyridazinyl-( 3)-thionophosphonic acid ester of the formula c H s e 5 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3 391 54 Dated 311116 2 1975 Inventor(s) 'l' Lorenz et 3.1.

It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

The term of this patent subsequent to April 15, 1992 has been disclaimed.

Signal and ,bcalcd this twenty'second Day Of June 1976 [SEAL] A nest:

RUTH C. MASON C. MARSHALL DANN Arresting ()fj'icrr Commissioner ojPatems and Trademarks 

1. AN O-ALKYL-O-6-(P-HALOGENOPHENYL)-PYRIDAZINYL(3)THIONOPHOSPHORIC(PHOSPHONIC) ACID ESTER OF THE FORMULA
 2. A compound according to claim 1, in which R is lower alkyl; R1 is lower alkyl or lower alkoxy of 1 to 4 carbon atoms or phenyl.
 3. The compound according to claim 1 wherein such compound is O, O-diethyl-O-6-(p-chlorophenyl)-pyridazinyl-(3)-thionophosphoric acid ester of the formula
 4. The compound according to claim 1 wherein such compound is O, O-diethyl-O-6-(p-bromophenyl)-pyridazinyl-(3)-thionophosphoric acid ester of the formula
 5. The compound according to claim 1 wherein such compound is ethyl-O-ethyl-O-6-(p-bromophenyl)-pyridazinyl-(3)-thionophosphonic acid ester of the formula
 6. The compound according to claim 1 wherein such compound is ethyl-O-ethyl-O-6-(p-chlorophenyl-pyridazinyl)-3)-thionophosphonic acid ester of the formula
 7. The compound according to claim 1 wherein such compound is phenyl-O-ethyl-O-6-(p-chlorophenyl)-pyridazinyl-(3)-thionophosphonic acid ester of the formula 